Field of the Invention
The present invention relates to a novel process for preparing substituted anthranilic acid derivatives of the formula (I)
in which                R1 is optionally singly or multiply, identically or differently fluorine- or chlorine-substituted C1-C6-alkyl, or C6-C10-aryl, or is a hetaryl radical of the general formula (II)        
                R1 is preferably C1-C3-alkyl, C6-aryl or a hetaryl radical of the general formula (II),        R1 is more preferably C1-C2-alkyl or a hetaryl radical of the general formula (II),where        R8 is C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, which may optionally be mono- or polysubstituted identically or differently by fluorine or chlorine, or is fluorine, chlorine, cyano, alkylamino, dialkylamino, cycloalkylamino or C3-C6-trialkylsilyl,        R8 is preferably fluorine, chlorine or C1-C6-alkyl,        R8 is more preferably fluorine or chlorine,        Z is CH or N,        Z is preferably and more preferably N,and        Y is hydrogen, fluorine, chlorine, optionally singly or multiply, identically or differently fluorine- or chlorine-substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, or is cyano, alkylamino, dialkylamino, cycloalkylamino, C3-C6-trialkylsilyl or a radical of the general formula (III)        
where                R9 is C1-C5-alkyl which may optionally be mono- or polysubstituted identically or differently by halogen,        R9 is preferably C1-C3 perfluoroalkyl,        R9 is more preferably CF3 or C2F5,        R2 is an OR5 or NR6R7 radical,        R2 is preferably and more preferably OR5,        R2 is likewise preferably and more preferably NR6R7,where        R5, R6 and R7 are each independently hydrogen, C1-C6-alkyl, or C6-C10-aryl,        R5, R6 and R7 are preferably each independently hydrogen, C1-C3-alkyl or C6-aryl,        R5, R6 and R7 are more preferably each independently hydrogen or C1-C2-alkyl,        R3 is hydrogen, optionally singly or multiply, identically or differently fluorine- or chlorine-substituted C1-C6-alkyl, C1-C6-alkoxy or C3-C6-cycloalkyl,        R3 is likewise halogen,        R3 is preferably C1-C5-alkyl,        R3 is more preferably methyl, ethyl or tert-butyl,        R3 is likewise preferably and more preferably chlorine,        R4 is hydrogen, fluorine, chlorine, cyano, optionally singly or multiply, identically or differently fluorine- or chlorine-substituted C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, di(C1-C4-alkyflamino, C3-C6-cycloalkylamino, (C1-C4-alkoxy)imino, (C1-C4-alkyl)(C1-C4-alkoxy)imino, SF5 or C3-C6-trialkylsilyl,        R4 is preferably hydrogen, chlorine or cyano,        R4 is more preferably chlorine or cyano,characterized in that substituted anthranilic acid derivatives of the formula (IV)        
in which the R1, R3 and R4 radicals are each as defined above and                X is chlorine, bromine or iodine, preferably bromine or iodine, more preferably bromine,are reacted in the presence of a palladium catalyst and optionally of a phosphine ligand simultaneously with carbon monoxide and a compound of the general formula (V)R5—OH   (V)in which R5 is as defined aboveor a compound of the general formula (VI)HNR6R7   (VI)in which R6 and R7 are each as defined above.        
Description of Related Art
The literature already states that it is possible to obtain substituted anthranilic acid derivatives of the formula (I) by reaction of anthranilic acid derivatives of the general formula (VII)
with carboxylic acids of the general formula (VIII)R1—COOH   (VIII)in the presence of agents which activate the carboxyl group for the desired reaction, for example thionyl chloride, oxalyl chloride, phosgene, methanesulphonyl chloride or toluenesulphonyl chloride (WO 2003/015519; WO 2003/106427; WO 2004/067528; WO 2006/062978; WO 2008/010897; WO 2008/070158; WO 2008/082502; WO 2009/006061; WO 2009/061991; WO 2009/085816; WO 2009 111553; Bioorg. & Med. Chem. Lett. 15 (2005) 4898-4906; Bioorg. & Med. Chem. 16 (2008) 3163-3170).
The known reactions can be illustrated by the following reaction schemes, where R1, R3, R4, R6 and R7 have, for example, the definitions given above:                a) R2═OR5 where R5 is not H, or NR6R7         
                b) R2═OR5 where R5═H        

These known methods for preparation of substituted anthranilic acid derivatives of the formula (I) require the availability of the corresponding substituted anthranilic acid derivatives of the general formula (VII). These substituted anthranilic acid derivatives of the general formula (VII) are either known or can be prepared by known organic chemistry methods. Some of these substituted anthranilic acid derivatives of the general formula (VII), however, can be prepared only in a complex manner, in multiple stages and at high cost, which can lead to uneconomically high costs for the end products as a result of unavoidable yield losses.
Substituted anthranilic acid derivatives of the formula (I) are of high interest as compounds having known insecticidal efficacy (see, for example, Bioorg. & Med. Chem. Lett. 15 (2005) 4898-4906; Biorg. & Med. Chem. 16 (2008) 3163-3170). Further, it is already known, that substituted anthranilic acid derivatives of the general formula (VII) can be obtained by reacting substituted anthranilic acid derivatives of the general formula (IX) with carbon monoxide in the presence of a palladium catalyst, of a ligand, of a primary amine and a base (WO 2012/103436). However, it is not known whether anthranilic acid amides of the general formula (IV) can be used correspondingly.